JP6820233B2 - A polymer, a resist composition containing the polymer, and a method for producing a device using the polymer. - Google Patents

Description

Some aspects of the invention relate to polymers used in resist compositions. In addition, some aspects of the present invention relate to a resist composition containing the polymer and a method for producing a device using the resist composition.

In recent years, the manufacture of display devices such as liquid crystal displays (LCDs) and organic EL displays (OLEDs) and the formation of semiconductor elements have been actively carried out by making full use of photolithography technology using photoresists. Light having a wavelength of 365 nm, h-rays (405 nm) and g-lines (436 nm) having a wavelength longer than that is widely used as active energy rays in the above-mentioned electronic parts and packages of electronic products.

With the increasing integration of devices, the demand for miniaturization of lithography technology is increasing. KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), ultrashort ultraviolet (EUV, wavelength 13.5 nm) and electron beam. Light with a very short wavelength, such as (EB), tends to be used for exposure. Since the lithography technique using light having a short wavelength, particularly EUV or electron beam, can be manufactured by single patterning, there is a need for a resist composition showing high sensitivity to EUV or electron beam or the like. It is expected to increase further in the future.

As the wavelength of the exposure light source is shortened, the resist composition is required to have improved sensitivity to the exposure light source and lithographic characteristics of resolvability capable of reproducing a pattern of fine dimensions. A chemically amplified resist is known as a resist composition satisfying such a requirement (Patent Document 1).
However, in the conventional chemically amplified resist, it is difficult to sufficiently suppress the reduction of the resist pattern collapse and the line edge roughness (LER) of the line pattern as the resolution line width of the resist becomes finer. In order to suppress the collapse of the resist pattern, there is a method of increasing the mechanical strength by cross-linking using a negative type chemically amplified resist. A chemically amplified negative resist using a cross-linking agent forms an ester or ether bond between the cross-linking agent and the base resin component in the presence of an acid. As a result, a negative pattern can be formed, but uncrosslinked carboxyl groups and phenolic hydroxyl groups remain in the exposed portion, so that these swell during alkaline development, causing defects such as bridging and a rounded resist. There is a drawback that it becomes a pattern shape. There is a strong demand for prevention of resist pattern collapse and bridge formation, but conventional chemically amplified resist compositions for EUV or electron beam have low absorption of EUV or electron beam, and have high sensitivity, resolution and pattern performance. It is difficult to satisfy the characteristics at the same time.

Japanese Unexamined Patent Publication No. 9-90637 Japanese Unexamined Patent Publication No. 2000-206694 SPIEA Advances in Resist Technology and Processing XV 3333,417 (1998)

It is an object of some aspects of the present invention to provide a polymer used for a resist composition having high absorption efficiency of particle beams or electromagnetic waves, particularly electron beams or EUV, and excellent characteristics of sensitivity, resolution and pattern performance. To do.
It is an object of some aspects of the present invention to provide a resist composition containing the polymer and a method for producing a device using the resist composition.

As a result of diligent studies to solve the above problems, the present inventors have made a unit A having an onium salt structure, electromagnetic waves such as EUV rather than carbon atoms, and metal atoms having high particle beam absorption such as electron beam and ion beam. Alternatively, it has been found that the above-mentioned problems can be solved by using a unit B having a structure containing an antimetal atom and a polymer containing the antimetal atom as the polymer of the resist composition. That is, by irradiating the resist composition containing the polymer with particle beams, electromagnetic waves, or the like, secondary electrons are generated from the unit B. Then, in addition to the polar conversion that becomes a non-ionic compound by decomposing the onium salt structure of the unit A by the secondary electron, the conjugate base bonded to the polymer from the unit A (hereinafter referred to as "polymer type conjugate base"). ) And hydrogen cations form a pair. By causing a cross-linking reaction between the polymer-type conjugated base and the above-mentioned unit B having reactivity, it is possible to construct a photoresist pattern having a high cross-linking density by the reaction between functional groups bonded to the polymer main chain. We have succeeded in increasing the sensitivity and suppressing pattern collapse with less swelling than the technique, and have completed some aspects of the present invention.

One aspect of the present invention that solves the above problems is a polymer containing a unit A and a unit B, wherein the unit A has an onium salt structure having an anion portion and a cation portion, and is a particle beam or an electromagnetic wave. It is a unit that generates a pair of polymer-type conjugated base and hydrogen cation by irradiation, and the onium salt structure is covalently bonded to the polymer main chain either directly or via the first spacer.
The unit B has a structure containing a metal atom or a metalloid atom, and the structure of the unit B is covalently or coordinated to the polymer main chain directly or via a second spacer.
When the structure of the unit B is covalently bonded to the polymer chain, the polymer-type conjugate base is added or substituted with the metal atom or metalloid atom to form an acid ester structure or an ion pair. Or,
When the structure of the unit B is coordinated to a polymer chain, the structure of the unit B has a coordinating substituent, and the polymer-type conjugated base and the coordinating substituent are coordinated. It is a polymer characterized in that a crosslinked structure is constructed by forming a complex structure by a child exchange reaction.
Examples of the metal or metalloid atom include B, Al, Si, As, Ti, Zr, Mo, Se, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rh, Pd, Ag. , Cd, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po and At.

One aspect of the present invention is a resist composition containing the above polymer.
Further, one aspect of the present invention is a step of forming a resist film on a substrate using the resist composition, a step of exposing the resist film using particle beams or electromagnetic waves, and a step of exposing the exposed resist film. It is a method of manufacturing a device including a step of developing and obtaining a photoresist pattern.

When used as a resist composition, the polymer according to some aspects of the present invention has high absorption efficiency of particle beams, electromagnetic waves, etc., and is excellent in sensitivity, resolution, and pattern performance characteristics.

In the present invention, the "particle beam or electromagnetic wave" includes an electron beam, extreme ultraviolet rays, and the like.
In the present invention, "by particle beam or electromagnetic wave irradiation" means exposing at least a part of the polymer to particle beam or electromagnetic wave. Exposure of a portion of the polymer to particle beams or electromagnetic waves excites or ionizes certain portions of the polymer, producing active species. The active species causes a secondary reaction such as decomposition of a part of the unit, addition of the active species to the unit, or desorption of hydrogen of the unit by the active species, and radicals are generated. Occur. Here, the "active species" refers to acids, radical cations, radicals, electrons and the like.
In the present invention, the "polymer-type conjugate base" is a conjugate base covalently bonded to the polymer main chain directly or via a spacer, and examples thereof include an anion portion of a sulfonic acid and an anion portion of a carboxylic acid.
In the present invention, the "paired state" may be a case where a polymer-type conjugate base and a hydrogen cation are dissociated or a case where they are bonded. The dissociation occurs when the acid generated by the decomposition of the onium salt structure is a strong acid, and specifically, when the anion portion of the onium salt structure has, for example, a sulfonate structure. The case of being bonded is when the acid generated by decomposing the onium salt structure is a weak acid, and when the anion portion of the onium salt structure has a carboxylate structure or the like.
Hereinafter, the present invention will be specifically described, but the present invention is not limited thereto.

<1> Polymer A polymer according to some aspects of the present invention has a unit A and a unit B. The unit A is a unit A having an onium salt structure having a cation part and an anion part, and generates a state in which a polymer-type conjugate base and a hydrogen cation are paired by irradiation with a particle beam or an electromagnetic wave, and the onium The salt structure is covalently attached to the polymer backbone, either directly or via a first spacer.
The unit B has a structure containing a metal atom or a metalloid atom (hereinafter, also referred to as a “metal-containing structure”), and the metal-containing structure is covalently bonded or arranged to the polymer main chain directly or via a second spacer. Coordinated.
When the metal-containing structure is covalently bonded to the polymer chain, the polymer-type conjugated base forms an acid ester structure or an ion pair by adding or substituting with the metal atom or semi-metal atom, or When the metal-containing structure is coordinated to a polymer chain, the metal-containing structure has a coordinating substituent, and the polymer-type conjugated base and the coordinating substituent undergo a ligand exchange reaction. A crosslinked structure is constructed by forming a complex structure.

The polymer containing the unit A and the unit B is exposed to at least a part of the polymer with a particle beam or an electromagnetic wave, and the reduction of the unit A produces a state in which a polymer-type conjugate base and a hydrogen cation are paired. To do. The polymer-type conjugate base reacts with the metal-containing structure of the unit B to form a covalent bond, an ionic bond, or a coordination bond, and a crosslinked structure can be constructed.

(Unit A)
The unit A has an onium salt structure having a cation part and an anion part, and when at least a part of the polymer is exposed to a particle beam or an electromagnetic wave, the polymer-type conjugate base and a hydrogen cation are paired. It creates a state. That is, the polymer main chain and the anion portion of the onium salt structure are covalently bonded directly or via the first spacer, and the polymer-type conjugated base derived from the anion portion bonded to the polymer main chain by the reduction of the onium salt structure and hydrogen. There is no particular limitation as long as it produces a state in which a cation is paired. Specific examples of the unit A having the onium salt structure include those represented by the following general formulas (1) and (2). However, it is not limited to these.
In the unit A represented by the general formulas (1) and (2), L ¹ and R ² correspond to the first spacer.

In the above general formulas (1) and (2), R ¹ is any one selected from the group consisting of a hydrogen atom; a fluorine atom; and a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. Yes, the alkyl group in R ¹ may have a substituent.

Examples of the alkyl group of R ¹ include linear alkyl groups such as methyl group, ethyl group, n-propyl group and n-butyl group;
Branched alkyl groups such as isopropyl group and t-butyl group;
Cyclic alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group; and the like.
Examples of the substituent that R ¹ may have (hereinafter, also referred to as “first substituent”) include a halogen atom such as fluorine.
When fluorine is used as the first substituent, as R ¹ , for example, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, 1,1,2,2,2- Examples thereof include a pentafluoroethyl group.
R ¹ preferably has 1 to 6 carbon atoms, and more preferably 1 to 2. When R ¹ has a first substituent, the number of carbon atoms shall include the first substituent.

When a carbon-carbon single bond is contained in R ¹ , at least one of the carbon-carbon single bonds may be replaced with an unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond. Examples of R ¹ having an unsaturated bond include a vinyl group and an isopropenyl group.
When having a methylene group in R ¹ , at least one of the above methylene groups may be substituted with a divalent heteroatom-containing group. The divalent heteroatom-containing group will be described later in R ² .

R ² is not particularly limited as long as the polymer main chain and the anion portion of the onium salt structure can be bonded via the above L ¹ , but for example, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms; heteroarylene group and the carbon atoms from 4-14; arylene group having 6 to 14 carbon atoms is any one selected from the group consisting of an alkylene group, an arylene group and heteroarylene group is a substituent in R ² May have.

Examples of the linear alkylene group having 1 to 12 carbon atoms of R ² include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group and n. Examples thereof include a-octylene group, an n-nonylene group, an n-decylene group, an n-undecylene group and an n-dodecylene group.
Examples of the branched alkylene group having 1 to 12 carbon atoms, R ^2, isopropylene group, isobutylene group, tert- butylene, isopentylene, hexylene group and the like to tert- pentylene and 2-ethyl.
Examples of the cyclic alkylene group having 1 to 12 carbon atoms of R ² include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group and a cyclohexylene group.

When a carbon-carbon single bond is contained in R ² , at least one of the carbon-carbon single bonds may be replaced with an unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond.
Examples of R ² having an unsaturated bond include a linear alkenylene group such as an ethynylene group, a propenylene group, a butenylene group, a hexenylene group, an octenylene group and a decanylene group;
Isopropenylene group, 1-ethylethenylene group, 2-methylpropenylene group, 2,2-dimethylbutenylene group, 3-methyl-2-butenylene group, 3-ethyl-2-butenylene group, 2-methyloctenylene Branched alkenylene groups such as groups and 2,4-dimethyl-2-butenylene groups;
Examples thereof include a cyclic alkenylene group such as a cyclopropenylene group, a cyclobutenylene group, a cyclopentenylene group and a cyclohexenylene group.

The arylene group having 6 to 14 carbon atoms, R ^2, pentalene, indene, naphthalene, azulene, heptalene, biphenylene, indacene, acenaphthylene, fluorene, phenalene, phenanthrene, anthracene, fluoranthene, acephenanthrylene, aceanthrylene, Divalent obtained by removing two hydrogen atoms from triphenylene, pyrene, chrysene, naphthalene, pyrene, perylene, pentaphene, pentacene, tetraphenylene, hexaphene, hexacene, rubicene, coronen, trinaphthylene, heptaphene, heptacentene, pyranthrene, ovalene and the like. Aromatic hydrocarbon groups of.
The heteroarylene group having a carbon number of 4 to 14 of R ^2, with the exception of furan, thiophene, imidazole, pyrazole, oxazole, pyridine, pyrimidine, quinoline, xanthene, carbazole, and the color two hydrogen atoms, such as acridyl obtained The divalent aromatic heterocyclic group to be used is mentioned.

It is preferable that part or all of the hydrogen contained in R ² is replaced with a fluorine atom.
When R ² has a methylene group, at least one of the methylene groups may be substituted with a divalent heteroatom-containing group.
Examples of the divalent heteroatom-containing group include -O-, -CO-, -COO-, -OCO-, -O-CO-O-, -NHCO-, -CONH-, and -NH-CO-O-. , -O-CO-NH-, -NH-, -N (R ^b ) (R ^b is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent. ), -N (Ar ^b )-(Ar ^b is an aryl group having 4 to 14 carbon atoms which may have a substituent), -S-, -SO- and -SO _2-, etc. Examples include groups selected from the group consisting of.
Examples of the linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, which is R ^b , are the same as those exemplified in R ^{3 to} R ⁵ described later.
Examples of the aryl group having 1 to 12 carbon atoms, which is Ar ^b , are the same as the aryl group exemplified in R ^{3 to} R ⁵ described later.

Examples of the substituent (hereinafter, also referred to as “second substituent”) that R ² may have include a hydroxy group, a cyano group, a mercapto group, a carboxy group, and an alkoxy group (-” in addition to the first substituent. OR ⁶ ), acyl group (-COR ^b ), alkoxycarbonyl group (-COOR ^b ), aryl group (-Ar ^b ), aryloxy group (-OAr ^b ), amino group, alkylamino group (-NHR ^b ), Dialkylamino group (-N (R ⁶ ) ₂ ), arylamino group (-NHAr ^b ), diarylamino group (-N (Ar ^b ) ₂ ), N-alkyl-N-arylamino group (-NR ^b Ar ^b) ), Phosphino group, silyl group, halogen atom, trialkylsilyl group (-Si- (R ^b ) ₃ ), silyl group in which at least one of the alkyl groups of the trialkylsilyl group is substituted with Ar ^b , alkylsulfanyl group. (-SR ^b ), arylsulfanyl group (-SAR ^b ) and the like can be mentioned, but are not limited thereto.
Examples of R ^b and Ar ^b in the second substituent include those similar to R ^b and Ar ^b in the divalent heteroatom-containing group.
The number of carbon atoms of R ² is, if R ² has a second substituent, and that including the second substituent.

L ¹ is not particularly limited as long as the polymer main chain and the anion portion of the onium salt structure can be bonded via R ² , but for example, direct bond; carbonyloxy group; carbonylamino group; linear, branched or cyclic. Any of the group selected from the group consisting of an alkylene carbonyloxy group; a linear, branched or cyclic alkylene carbonyl amino group; an arylene carbonyloxy group; and an arylene carbonylamino group; the amino group, the alkylene group and the L ¹ in L ^1. The arylene group may have a substituent (hereinafter, also referred to as “third substituent”).
The arylene group in L ¹ may be a heteroarylene group.
Examples of the third substituent include an alkyl group, a hydroxy group, a mercapto group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylsulfanylcarbonyl group, an arylsulfanyl group, and an alkylsulfanyl group. Aryl group, heteroaryl group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, arylsulfonyl group, (meth) acryloyloxy group, hydroxy (poly) alkyleneoxy group, amino group, cyano It is any one selected from the group consisting of a group, a nitro group and a halogen atom.

When L ¹ is an alkylene group or a group having an alkylene group, specific examples of the alkylene group include those similar to the alkylene group exemplified in R ² described later.
When L ¹ is an arylene group or a group having an arylene group, specific examples of the arylene group include those similar to the arylene group and the heteroarylene group exemplified in R ² described later.
When L ¹ has a carbon atom, the number of carbon atoms including the third substituent is preferably 1 to 12.

Examples of the structure represented by the general formula (1) include a structure having a sulfonate shown below.

Examples of the structure represented by the general formula (2) include a structure having a carboxylate shown below.

M ⁺ is a sulfonium cation represented by the general formula (3) or an iodonium cation represented by the general formula (4).
The structure of the cation portion M ⁺ of the onium salt is a sulfonium cation or an iodonium cation, and specific examples thereof include those represented by the following general formulas (3) and (4).

R ^{3 to} R ⁵ are linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms, which may have substituents, respectively; aryl groups having 6 to 14 carbon atoms which may have substituents; It is any one selected from the group consisting of heteroaryl groups having 4 to 14 carbon atoms which may have a substituent.
R ³ and R ⁴ form a ring structure with a sulfonium cation or an iodonium cation to which they are bonded, either directly in a single bond or via one selected from the group consisting of an oxygen atom, a sulfur atom and a methylene group. You may.
When a methylene group is contained in R ^{3 to} R ⁵ , at least one of the methylene groups may be substituted with the above divalent heteroatom-containing group.

The linear alkyl group having 1 to 12 carbon atoms of R ^{3 to} R ⁵ includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group and an n-heptyl group. , N-octyl group, n-nonyl, n-decyl group, n-undecyl, n-dodecyl and the like.
Examples of the branched alkyl group having 1 to 12 carbon atoms of R ^{3 to} R ⁵ include an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a tert-pentyl group and a 2-ethylhexyl group. Can be mentioned.
The cyclic alkyl group having 1 to 12 carbon atoms of R ^{3 to} R ⁵ includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantane-1-yl group, an adamantane-2-yl group, and norbornane-1-. Examples thereof include an yl group and a norbornane-2-yl group.

When a carbon-carbon single bond is formed in R ^{3 to} R ⁵ , even if at least one of the carbon-carbon single bonds is replaced with an unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond. Good. Examples of R ^{3 to} R ⁵ having an unsaturated bond include linear alkenyl groups such as vinyl group, allyl group, 3-butenyl group, 1-methylallyl group, 2-methylallyl group, 4-pentenyl group and 5-hexenyl group. ;
Isopropenyl group, isobupenyl group, 3-butenyl group, 2-butenyl group, isopentenyl group, 2-ethyl2-hexenyl group, neopentenyl group, isohexenyl group, isotridecenyl group, isooctadecenyl group and isotoriaconte Branched alkenyl groups such as Nyl group;
Cyclic alkenyl groups such as cyclopentenyl group, cyclobutenyl group, cyclopentenyl group and cyclohexenyl group; and the like can be mentioned.

The aryl groups having 6 to 14 carbon atoms of R ^{3 to} R ⁵ include a phenyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, a naphthyl group, an anthryl group, a phenanthrenyl group, a pentarenyl group, an indenyl group and an indaceyl group. , Acenaphthyl group, fluorenyl group, heptalenyl group, naphthacenyl group, pyrenyl group, chrysenyl group, tetrasenyl group and the like.
Heteroaryl groups having 4 to 14 carbon atoms of R ^{3 to} R ⁵ include a furanyl group, a thienyl group, a pyranyl group, a sulfanyl pyranyl group, a pyrrolyl group, an imidazolyl group, an oxazolyl group, a thiazolyl group, a pyrazoyl group and a pyridyl group. , Pyrimidyl group, isobenzofuranyl group, benzofuranyl group, isochromenyl group, chromenyl group, pyrazil group, prynyl group, quinolinyl group, isoquinolinyl group, chromenyl group, thianthrenyl group, dibenzothiophenyl group, phenothiazine group, phenoxadinyl group, phenoxadinyl Examples thereof include a group, a phenazinyl group, an indolyl group, an isoindryl group, a benzoimidazolyl group, a xanthenyl group, an aquazinyl group and a carbazoyl group.

R ^{3 to} R ⁵ may have a substituent (hereinafter, also referred to as “fourth substituent”), and examples of the fourth substituent include those similar to the above-mentioned third substituent.
R ³ to R number of carbon atoms of the ^5, if R 3 to R ⁵ has a fourth substituent, and that including the fourth substituent.

Examples of the sulfonium cation and the iodonium cation as the cation portion of the onium salt structure include those having the structure shown below.

(Unit B)
The structure of the unit B has a structure containing a metal atom or a semi-metal atom, and the structure is covalently or coordinated to the polymer main chain directly or via a second spacer, and the structure is a polymer. When covalently bonded to the chain, the polymer-type conjugated base forms an acid ester structure or ion pair by adding or substituting with the metal atom or semi-metal atom, or the structure is attached to the polymer chain. When coordinated, the structure has a coordinating substituent, and the polymer-type conjugated base and the coordinating substituent undergo a ligand exchange reaction to form a complex structure, thereby forming a crosslinked structure. There are no particular restrictions as long as the body is constructed.
The ratio of the unit A to the unit B in the polymer is preferably 5:95 to 95: 5.

As the metal atom or metalloid atom, it is preferable that the absorption of particle beams or electromagnetic waves is higher than that of the carbon atom, and the absorption of the EUV, electron beam or ion beam is higher than that of the carbon atom. preferable. Specific examples of such metal atoms or metalloid atoms include B, Al, Si, As, Ti, Zr, Mo, Se, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, and Ga. , Ge, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po and At. At least one selected atom is preferred. The metal atom or metalloid atom preferably has high absorption to EUV, electron beam or ion beam, but is exemplified above if it reacts with the polymer-type conjugated base to construct a crosslinked structure. It may be a metal other than. Preferably, it is any atom selected from the group consisting of Sn, Sb, Ge, Bi and Te.
Since the polymer contains the unit B, it contains atoms having a higher specific gravity than carbon and oxygen, and contains atoms that absorb a particle beam such as an electron beam or an electromagnetic wave such as EUV, which is particularly high among electromagnetic waves. It is possible to improve the efficiency of secondary electron generation when irradiated with EUV. As a result, the sensitivity of the resist can be increased.

The structure of the unit B is at least one of the structures represented by the following general formulas (5) to (7).
In the unit B represented by the general formula (5), L ¹ and R ² correspond as the second spacer.
In the unit B represented by the general formulas (6) and (7), L ¹ , R ² and C ¹ correspond to the second spacer.

In the general formulas (5) to (6), R ¹ , R ² and L ¹ are independently selected from the same options as R ¹ , R ² and L ^{1 in the} general formula (1).
R ⁶ is selected from the same options as above R ^5, 2 or more in the case with R ⁶ R ⁶ each other directly or an oxygen atom, a nitrogen atom, through one of a sulfur atom and a methylene group to form a ring You may.
X is the metal atom or metalloid atom.

h has a valence of X of -1 and 0 to 3.
i is 1 to 6, j is 0 to 5, and is determined by the valence of X and the coordination state of C ¹ and C ² .
k is 0 to 5, and is determined by the valence of X and the coordination state of C ¹ .
In the general formulas (6) and (7), → indicates a coordination bond.

As the structure represented by the above general formula (5), alkyltin, aryltin, alkylantimony, arylantimony, alkylgerman, arylgerman, alkylbismucin, arylbismucin, alkyltellite having high absorption to particle beams or electromagnetic waves It is preferable that any structure selected from the group consisting of and aryltellite is a unit bonded to the * portion of the following general formula (15) at any position of the structure.
In the general formula (5), two or more of the above R ² and the plurality of R ⁶ are bonded either directly by a single bond or via one selected from the group consisting of methylene groups. A ring structure may be formed together with X.

In the general formula ^(15), R 1, ^{R 2} and ^{L 1} is selected from the same options as ^R 1, ^{R 2} and ^{L 1} in formula (1).

As the unit B, the units represented by the following general formulas (16) to (22) are preferable because they can be synthesized particularly easily.

In the general formulas (16) to (22), R ¹ , R ² , R ⁶ and L ¹ are selected from the same options as in the general formula (5).

Specifically, the unit B includes 4-vinylphenyl-triphenyltin, 4-vinylphenyl-tributyltin, 4-isopropenylphenyl-triphenyltin, 4-isopropenylphenyl-trimethyltin, trimethyltin acrylate, and acrylic acid. Tributyltin, triphenyltin acrylate, trimethyltin methacrylate, tributyltin methacrylate, triphenyltin methacrylate, 4-vinylphenyl-diphenylantimony, 4-isopropenylphenyl-diphenylantimony, 4-vinylphenyl-triphenylgerman, 4 -Vinylphenyl-tributylgerman, 4-isopropenylphenyl-triphenylgerman and 4-isopropenylphenyl-trimethylgerman, 4-vinylphenyl-triphenylsilane, (1-fluorovinyl) methyldiphenylsilane, 4-vinylphenylboron Examples thereof include units composed of monomers such as acid 1,3-propanediol and 4-vinylphenylboronic acid catechol.

To construct a crosslinked structure by reaction of the polymeric conjugate base and unit B de Hanareno from X of R ⁶ be similar or higher and R ² covalently attached via L ¹ to the polymer backbone Is desirable. De Hanareno of R ⁶ from X as a method of increasing than R ^2, or that R ² R ⁶ has many electron-donating group than R ² has many electron attractive group than R ⁶ Is preferable.
Examples of the electron donating group of R ⁶ include an alkyl group, an alkenyl group, an alkoxy group (-OR ^3a ) and an alkylthio group (-SR ^3a ) bonded to the ortho-position or para-position of the aryl group; and the like. For example, when R ² is a phenylene group, R ⁶ is preferably a 4-alkylphenyl group, a 4-alkoxyphenyl group, a 4-alkylsulfanylphenyl group, a 4-dialkylaminophenyl group or the like.
The electron-withdrawing group of R ² is based on an acyl group, an acyloxy group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfonyloxy group, an arylsulfonyloxy group, a nitro group, a nitroso group, a trifluoromethyl group and an aryl group. Any one selected from the group consisting of an alkoxy group substituted with a meta position, an aryloxy group, an alkylsulfanyl group and an arylsulfanyl group and the like can be mentioned. For example, when R ⁶ is a phenyl group, R ² is preferably a ² -acylphenylene group, a 3-cyanophenylene group, a 2,3,5,6, -tetrafluorophenylene group and the like, but the present invention is not limited thereto.

C ¹ in the structure represented by the general formula (6) is a monodentate ligand or a polydentate ligand covalently bonded to R ² , and is a monovalent organic group having at least one coordination atom.
C ² is an independent monodentate ligand or an independent polydentate ligand as the coordinating substituent, and is a molecule having at least one coordinating atom. Specific examples of C ² include the following.
Examples of the independent monodentate ligand of C ² include molecules such as cyanide, cyanate, isothiocyanate, and a hydrocarbon compound containing π electrons. C The ^second independent polydentate ligand, such as those shown above coordinating atoms in the molecule and represented by the following general formula has two or more (23) are exemplified, but the present invention is not limited thereto.
R ^19- (Y) _k (23)
The one represented by the above general formula (23) has the same structure, or when it has s active protons such as a hydroxy group or electron-withdrawing group α-position protons such as a carbonyl group, s of them are eliminated. It can be a polydentate ligand as the s-valent anion structure to be produced. s is an integer from 0 to 4.

Hydrocarbon compounds containing π electrons include chain olefins such as ethylene and propylene, and cyclic olefins such as cyclopentene, cyclohexene and norbornene;
Chain dienes such as butadiene and isoprene;
Cyclic diene such as cyclopentadiene, methylcyclopentadiene, pentamethylcyclopentadiene, cyclohexadiene and norbornadiene;
Aromatic hydrocarbons such as benzene, toluene, xylene, hexamethylbenzene, naphthalene and indene; and the like.

In the general formula (23), R ¹⁹ is a k-valent organic group which may have a substituent and at least one methylene group may be substituted with the divalent heteroatom-containing group. , Y are -OH, -COOH, -NCO, -PR ^a ₂ , -P (OR ^a ) ₂ , -P (O) R ^a ₂ , -SO ₃ H, -COOR ^a or -NHR ^a . ^Ra is a monovalent alkyl group having 1 to 12 carbon atoms in which a hydrogen atom or a hydrogen atom may be replaced with a fluorine atom, an aryl group having 6 to 14 carbon atoms, and a heteroaryl having 4 to 14 carbon atoms. It is the basis. k is an integer of 1 to 4. When k is 2 or more, a plurality of Ys may be the same or different. ^Ra is selected from the same options as R ³ above.
The substituent that R ¹⁹ may have is the same option as the substituent (third substituent) of L ^{1 in} the above general formula (1).

Examples of the k-valent hydrocarbon group include alkanes such as methane, ethane, propane and butane;
Alkenes such as ethene, propene, butene and pentene;
Chain hydrocarbons with 1 to 30 carbon atoms such as alkynes such as ethine, propyne, butin and pentyne;
Alicyclic hydrocarbons having 3 to 30 carbon atoms such as cycloalkanes such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, and adamantan, cycloalkenes such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, and norbornene;
Hydrocarbons such as aromatic hydrocarbons having 6 to 30 carbon atoms such as benzene, toluene, xylene, mesitylene, naphthalene, methylnaphthalene, dimethylnaphthalene, anthracene and the like; groups obtained by removing k hydrogen atoms from the above, etc. Can be mentioned.

Examples of the above (23) include hydroxy esters such as glycolic acid ester, lactic acid ester, 2-hydroxycyclohexane-1-carboxylic acid ester, and salicylic acid ester, and acetylacetone, methylacetylacetone, ethylacetylacetone, 2,4-. Β-diketones such as pentandione, 3-methyl-2,4-pentandione, acetoacetate ester, α-alkyl substituted acetoacetate ester, β-ketopanoic acid ester, benzoylacetate ester, 1,3-acetone dicarboxylic acid ester Β-ketoesters such as, malonic acid diester, α-substituted malonic acid diester, α-cycloalkyl substituted malonic acid ester, β-dicarboxylic acid ester such as α-aryl substituted malonate ester, ethylene glycol, propylene glycol, butylene Glycol, hexamethylene glycol Diethylene glycol, dipropylene glycol, dibutylene glycol, triethylene glycol, dialkylene glycol such as tripropylene glycol;
Cycloalkylene glycols such as cyclohexanediol, cyclohexanedimethanol, norbornanediol, norbornanedimethanol, and adamantandiol;
Alcan triols such as 1,4-benzenedimethanol, 2,6-naphthalenedimethanol catechol, resorcinol, hydroquinone, glycerin, 1,2,4-butantriol;
Cycloalkane triols such as 1,2,4-cyclohexanetriol, 1,2,4-cyclohexanetrimethanol;
Alkanetetraols such as 1,2,4-benzenetrimethanol, 2,3,6-naphthalenetrimethanol, pyrogallol, 2,3,6-naphthalenetriol, erythritol, pentaerythritol;
1,2,4,5-Cyclohexanetetraol 1,2,4,5-benzenetetramethanol, polyols such as 1,2,4,5-benzenetetraol, oxalic acid, malonic acid, succinic acid, glutaric acid , Chain saturated dicarboxylic acid such as adipic acid;
Maleic acid, fumaric acid, 4-cyclohexanedicarboxylic acid, norbornandicarboxylic acid, adamantandicarboxylic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,2,3-propanetricarboxylic acid Acid, 1,2,3-propentricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, trimellitic acid, 2,3,7-naphthalenetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 1 , 2,3,4-butadiene tetracarboxylic acid, 1,2,5,6-cyclohexanetetracarboxylic acid, 2,3,5,6-norbornantetracarboxylic acid, pyromellitic acid, 2,3,6,7- Carboxylic acids such as naphthalenetetracarboxylic acid, ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexanediisocyanate, isophorone diisocyanate, tolylene diisocyanate, 1,4-benzenediisocyanate, 4,4'- Diphenylmethane diisocyanate, trimethylene triisocyanate, 1,2,4-cyclohexanetriisocyanate, 1,2,4-benzenetriisocyanate, tetramethylenetetraisocyanate, 1,2,4,5-cyclohexanetetraisocyanate, 1,2,4 , 5-benzenetetraisocyanate and other isocyanates, ethylenediamine, N-methylethylenediamine, N, N'-dimethylethylenediamine, trimethylenediamine, N, N'-dimethyltrimethylenediamine, tetramethylene, 1,4-cyclohexanediamine, 1, , 4-Di (aminomethyl) cyclohexane, 1,4-diaminobenzene, 4,4'-diaminodiphenylmethane, triaminopropane, N, N', N "-trimethyltriaminopropanediamine, N, N'-dimethyltetra Methylenediamine, 1,2,4-triaminocyclohexane, 1,2,4-triaminobenzene, tetraaminobutane, 1,2,4,5-tetraaminocyclohexane, 2,3,5,6-tetraaminonorbornane , 1,2,4,5-Tetraaminobenzene and other amines.

Specifically, as C ^{1 in the} structure represented by the general formula (6), an organic group obtained by removing one hydrogen atom from R ²⁶ of the general formula (23) is preferably mentioned.

Examples of the monomers constituting the structures represented by the general formulas (6) to (7) are as follows.

(Unit C)
The polymer in one embodiment of the present invention has an acid dissociable group in addition to the above units A and B, and the acid dissociable group is deprotected in the presence of an acid in which the onium salt structure is decomposed. This may further contain unit C, which increases the reactivity with unit B.
The content of the unit C in the polymer is preferably 0 to 4 molar equivalents with respect to the total amount of the units A and B.

Specific examples of the unit C include those listed by the following general formulas (8) to (11).

R ^{1, R 2} and ^{L 1} in the general formula (8) to (11) in is selected from the same options as ^R 1, ^{R 2} and ^{L 1} in the general formula (1).
R ⁷ is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent.
R ⁸ and R ⁹ are linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms, which may independently have a substituent.
Two or more of the above R ⁷ , R ⁸ and R ⁹ and may form a ring structure either directly in a single bond or through one selected from the group consisting of methylene groups.
R ¹⁰ is straight chain may have a substituent group, branched or cyclic alkyl group having 1 to 12 carbon atoms.
R ¹¹ and R ¹² are each independently selected from the group consisting of a hydrogen atom; and a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent. ..
Two or more of the above R ¹⁰ , R ¹¹ and R ¹² may form a ring structure either directly in a single bond or through one selected from the group consisting of methylene groups.
Each of R ¹³ is independently selected from the group consisting of an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an alkylsulfanyl group, an alkylsulfinyl group, an alkylsulfonyl group, an amino group, a cyano group, a nitro group and a halogen atom. If it is either and has a carbon as a substituent, they have a substituent.
When a carbon-carbon single bond is formed in R ^{7 to} R ¹³ , at least one of the above carbon-carbon single bonds may be replaced with a carbon-carbon double bond or a carbon-carbon triple bond.
When a methylene group is contained in R ^{7 to} R ¹³ , at least one of the above methylene groups may be substituted with a divalent heteroatom-containing group.
l ¹ is an integer of ¹ to 2, m ¹ is an integer of 0 to 4 when l ¹ is 1, and an integer of 0 to 6 when l ¹ is 2.
n ¹ is 1-5 when ^{l 1} is 1, and 1-7 integer when ^{l 1} is 2,
m ¹ + n ¹ is 1 to 5 when l ¹ is 1, and ¹ to 7 when l ¹ is 2.

Examples of R ^{8 to} R ¹⁰ include those similar to the above-mentioned alkyl group of R ³ . For example, methyl, ethyl, n-propyl, n-butyl, isopropyl, t-butyl, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantan-1-yl group, adamantan-2-yl group, norbornan-1-yl. Examples thereof include alkyl groups such as an yl group and a norbornan-2-yl group.
Examples of the alkyl group of R ^{11 to} R ¹² include those similar to the alkyl group of R ³ described above.

It is preferable that a part of the hydrogen atom of R ¹³ is substituted with a hydroxyl group, an alkoxy group, an oxo group, an amino group, an alkylamino group or the like.

Specifically, the structure shown below can be exemplified. However, the present invention is not limited to this.

(Unit D)
In addition to the above units A to C, the polymer in one embodiment of the present invention preferably contains a unit D that can act as a sensitizer and increase the sensitivity to particle beams and electromagnetic waves.
The content of the unit D in the polymer is preferably 0 to 1 molar equivalent with respect to the total amount of the units A and B.

The unit D is a compound represented by the following general formulas (12) to (14) bonded to R ² at the position of * in the general formula (15).

In the above general formulas (12) to (14), R ¹⁵ , R ¹⁶ and R ¹⁷ are independently selected from the group consisting of a hydrogen atom; an electron donating group; and an electron attracting group; And
At least one of R ¹⁴ and R ¹⁵ is the electron donating group, and at least one of R ¹⁶ is the electron donating group.
R ¹⁷ is any one selected from the group consisting of a hydrogen atom; and a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms which may have a substituent. The alkyl group of R ¹⁷ is selected from the same options as the alkyl group of R ³ .
R ¹⁸ is any of 2 independently selected from the group consisting of a hydrogen atom; and a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms which may have a substituent. One of R ¹⁸ may be bonded together to form a ring structure. The alkyl group of R ¹⁸ is selected from the same options as the alkyl group of R ³ .
When a carbon-carbon single bond is contained in R ^{14 to} R ¹⁸ , at least one of the carbon-carbon single bonds may be replaced with a carbon-carbon double bond or a carbon-carbon triple bond.
When a methylene group is contained in R ^{14 to} R ¹⁸ , at least one of the above methylene groups may be substituted with a divalent heteroatom-containing group.
E is any one selected from the group consisting of direct bonds, oxygen atoms; sulfur atoms and methylene groups.
m ³ is an integer of 0 or 1, n ⁵ and n ⁶ are integers of 0 to 2, respectively, n ⁵ + n ⁶ is 2, and when n ⁵ is 1, n ³ is 0 to 4. It is an integer, n ³ is an integer 0 to 6 when n ⁵ is 2, n ⁴ is an integer 0 to ⁴ when n ⁶ is 1, and n ⁴ is 0 to 6 when n ⁶ is 2. an integer, ^{n 7} is an integer of 0 to 7, ^{n 8} is 1 or 2, ^{n 7} when ^{n 8} is 1 is an integer of 0 to 5, when ^{n 8} is 2 ^{n 7} Is an integer from 0 to 7.

As the electron donating group of R ¹⁴ , R ¹⁵ and R ¹⁶ , the number of carbon atoms 1 to 12 alkyl group (-R ^c ) which may have a substituent; and the aromatic ring with respect to the hydroxyl group or acetal group. Alkoxy groups (-OR ^c ) and alkylthio groups (-SR ^c ) bonded to the ortho-position or para-position; and the like can be mentioned.

The R ^c is selected from the same options as the alkyl group as the R ³ . Further, one of a trimethylsilyl group hydrogen with an alkyl group R ^3, a silyl group-substituted alkyl group substituted by a trialkylsilyl group such as triethylsilyl group and dimethyl triethylsilyl group; in the alkyl group, the compound (11) Alkyl groups in which at least one of the hydrogen atoms of the carbon atom not directly bonded to the aromatic ring of (13) is substituted with a cyano group, a fluoro group, or the like; etc. are also preferably mentioned.

The electron-withdrawing groups of R ¹⁴ , R ¹⁵ and R ¹⁶ include -C (= O) R ^c ; -C (= O) Ar ^b ; -C (= O) OR ^c ; -SO ₂ R ^c ;- SO ₂ Ar ^b ; nitro group; nitroso group; trifluoromethyl group; meta-substituted with respect to hydroxyl or acetal group-OR ^c ; meta-substituted with respect to hydroxyl or acetal group-OR ²⁰ ( R ²⁰ is an optionally substituted alkylsulfanyl group, one selected from the group consisting of arylsulfanyl group and alkylsulfanyl phenyl group); substituted meta to the hydroxyl group or an acetal group - SR ^c ; -SAr ^b substituted with a meta position with respect to a hydroxyl group or an acetal group; above-C (= O) R ²¹ (R ²¹ may have some or all of hydrogen atoms substituted with fluorine atoms. A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms which may have a substituent; and 4 to 20 carbon atoms which may have a substituent. (I); a group in which at least one of the carbon-carbon single bonds in -C (= O) OR ^c , -SO ₂ R ^c and -SR ²¹ is substituted with a carbon-carbon double bond or Groups substituted with a carbon-carbon triple bond; etc.
The alkyl, aryl and heteroaryl groups of R ²¹ can be selected from the same options as R ³ .

As the compound represented by the general formula (12) to (14) is bonded to * in the R ² group of the general formula (15) include those shown, for example, in concrete below.

(Unit E)
In addition to the above units A to D, the polymer in one embodiment of the present invention acts as an acid propagating agent that produces sulfonic acid by a decomposition reaction accompanied by a dehydration reaction by the action of the polymer acid generated from the unit A. , It is preferable to contain a unit E (hereinafter, also referred to as "unit E") capable of increasing the sensitivity to particle beams and electromagnetic waves.

Examples of the unit E include compounds represented by the following general formulas (24a) to (24d).

R ^{24 to} R ²⁶ of the general formulas (24a) to (24d) are selected from the same options as R ³ represented by the general formulas (3) and (4), respectively, and like R ³ and R ⁴ , R ^24- R ²⁶ may form a ring structure with each other by a single bond and a direct bond, or via any one selected from the group consisting of an oxygen atom, a sulfur atom and a methylene group.
R ^{7 to} R ⁹ and R ^{18 of the} general formulas (24a) to (24d) are selected from the same options as R ^{7 to} R ⁹ and R ^{18 of the} general formulas (8) and (14), respectively.

Examples of the unit E include those having the structure shown below, but the present invention is not limited thereto.

The content of the unit E in the polymer is preferably 0 to 4 molar equivalents with respect to the total amount of the units A and B.

(Other units)
In addition to the above units A to E, the polymer in one embodiment of the present invention may have a unit usually used as a resist composition as long as the effects of the present invention are not impaired.
For example, a unit having a skeleton containing an ether group, a lactone skeleton, a sultone skeleton, a sulfolane skeleton, an ester group, a hydroxy group, an epoxy group, a glycidyl group, an oxetanyl group, etc. in the * portion of the general formula (15) (hereinafter, " (Also referred to as "unit F").

Examples of those containing a lactone skeleton; a sultone skeleton; and a sulfolane skeleton in the * portion of the general formula (15) can be exemplified below. However, the present invention is not limited to this.

The unit F having a hydroxy group in the * portion of the general formula (15) can serve as a hydrogen source when a state in which a polymer-type conjugate base and a hydrogen cation are paired is generated from the unit A, and is an acid. It is preferable because the generation efficiency can be improved and the sensitivity becomes high. More preferably, it has low reactivity with the unit B and can serve as a hydrogen source.

Examples of the unit F having a hydroxy group in the * portion of the general formula (15) include those shown below. However, the present invention is not limited to this.

Spin-on glass (SoG) in a photoresist that constructs a multilayer film having different etching resistance by incorporating the siloxane unit having high oxygen etching resistance as well as the unit B having high oxygen etching resistance by containing the siloxane unit in the polymer. ) It becomes easy to omit the layer and transfer the pattern directly to the SoC layer, so that the throughput can be improved. Therefore, it is also preferable to include a siloxane unit in addition to the above units A to F.

As the siloxane unit, silsessioxane (POSS) is preferable.

Examples of the siloses siloxane include acrylicol POSS, acrylic isobutyl POSS, methacrylic isobutyl POSS, methacrylate cyclohexyl POSS, methacrylate isobutyl POSS, methacrylate ethyl POSS, methacrylic ethyl POSS, methacrylate octyl POSS, methacrylic isooctyl POSS, and methacrylic phenyl. Examples include compounds such as POSS.

Further, by introducing silyl ethers such as a tris (trimethylsilyloxy) silyl group as shown in the following general formula (25) into the unit B, the etching resistance of the oxygen plasma is maintained high and the oxygen plasma is generated from the unit A. It is preferable that the crosslinks can be crosslinked by an acid-catalyzed hydrolysis reaction.

(Method of synthesizing compounds constituting each unit)
Some of the compounds constituting the unit A will be illustrated in Examples described later. Further, for example, it can also be obtained by applying Japanese Patent Application Laid-Open No. 2009-263487.
Some synthesis of the compounds constituting the unit B will be illustrated in Examples described later. Other methods include the following.
For example, when the unit B is represented by the general formula (6), the compound constituting the unit B includes a compound having a structure represented by the following general formula (26). The compound represented by the following general formula (26) is synthesized, for example, by the following method. First, a halide of the metal atom or metalloid atom X and a diamine covalently bonded to a polymerizable group having R ¹ via a part (L ¹ and R ² ) of the second spacer are covalently bonded in a solution. Mix to obtain a complex. Then, silver sulfate is added to filter out the precipitated silver chloride, and then oxalic acid and an aqueous sodium hydroxide solution are added and stirred overnight. By recovering the obtained precipitate, the compound represented by the following formula (26) can be obtained.

The unit C can be synthesized by a usual method for synthesizing a monomer having an acid dissociative group. For example, Japanese Patent Publication No. WO2009 / 110388 may be applied.
Some examples will be given in the synthesis of the above unit D and the examples described later. As another method, for example, WO2016 / 133073 can be mentioned.
The unit E can be synthesized by a usual method for synthesizing a monomer having a structure that acts as an acid growth agent. For example, the Journal of Photopolymer science and Technology 17 (2004) 427-432 may be applied.
The unit F can be synthesized by a usual method for synthesizing a monomer containing a lactone, a sultone skeleton, or the like. For example, Japanese Patent Application Laid-Open No. 2011-184390 may be applied.

<2> Resist Composition The resist composition according to one aspect of the present invention is characterized by containing the above polymer. In addition to the above polymer, components such as a sensitizing compound, an organometallic compound and an organometallic complex may be optionally contained. Hereinafter, each component will be described.

(Sensorizing compound)
The resist composition of one aspect of the present invention may have a structure containing only the above polymer, but in addition to the above polymer, other components, for example, the above general formulas (12) to (14) contained in the unit D. ) May be further contained alone, not as a unit of polymer. By containing these in the resist composition, it can act as a sensitizer and increase the sensitivity to particle beams or electromagnetic waves.

The content of the sensitizing compound in the resist composition is preferably 0 to 1 molar equivalent with respect to the total amount of the units A and B.

(Organometallic compounds and organometallic complexes)
The resist composition of one aspect of the present invention preferably further contains either an organometallic compound or an organometallic complex.
The metals include Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Xe, Hf, Ta, W, The unit A and the unit B are sensitized by being at least one selected from the group consisting of Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, At, Rn and Ra. It is preferable because it can be done.

Examples of the organometallic compound include tetraaryl tin, tetraalkyl tin, and bis (alkylphosphine) platinum.
Examples of the organic metal complex include hafnium acrylate (IV), zirconium acrylate (IV), bismuth acrylate (III), bismuth acetate (III), tin oxalate (II) and the like.
The blending amount of the organometallic compound and the organometallic complex in the resist composition is preferably 0 to 0.5 molar equivalent with respect to the unit A.

(Other ingredients)
In any of the embodiments, the resist composition according to one aspect of the present invention may contain other components as long as the effects of the present invention are not impaired. Examples of the components that can be blended include known additives such as a fluorine-containing water-repellent polymer, an acid diffusion control agent, a surfactant, a filler, a pigment, an antistatic agent, a flame retardant, a light stabilizer, and an antioxidant. At least one selected from an ion catching agent, an organic carboxylic acid, a dissolution inhibitor, a solvent and the like may be added.

Examples of the fluorine-containing water-repellent polymer include those usually used in an immersion exposure process, and those having a higher fluorine atom content than the polymer are preferable. Thereby, when the resist film is formed by using the resist composition, the fluorine-containing water-repellent polymer can be unevenly distributed on the surface of the resist film due to the water repellency of the fluorine-containing water-repellent polymer. ..

The above-mentioned surfactant is preferably used to improve the coatability. Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. Examples thereof include agents, fluorosurfactants, and organosiloxane polymers.

The content of the surfactant is preferably 0.0001 to 2 parts by mass, more preferably 0.0005 to 1% by mass, based on 100 parts by mass of the resist composition component.

The acid diffusion control agent has the effect of controlling the diffusion phenomenon of the acid generated from the photoacid generator in the resist film and controlling an unfavorable chemical reaction in the non-exposed region. Therefore, the storage stability of the obtained resist composition is further improved, the resolution of the resist is further improved, and the line width change of the resist pattern due to the fluctuation of the leaving time from the exposure to the development process can be suppressed. , A resist composition having excellent process stability can be obtained.

Examples of the acid diffusion control agent include a compound having one nitrogen atom in the same molecule, a compound having two nitrogen atoms, a compound having three nitrogen atoms, an amide group-containing compound, a urea compound, and a nitrogen-containing heterocyclic compound. Be done. Further, as the acid diffusion control agent, a photodisintegrating base that is exposed to exposure to generate a weak acid can also be used. Examples of the photodisintegrating base include onium salt compounds and iodonium salt compounds that are decomposed by exposure and lose their acid diffusion controllability.

Specifically, as the acid diffusion control agent, Japanese Patent Application Laid-Open No. 3577743, Japanese Patent Application Laid-Open No. 2001-215689, Japanese Patent Application Laid-Open No. 2001-166476, Japanese Patent Application Laid-Open No. 2008-102383, Japanese Patent Application Laid-Open No. 2010-243773, JP-A-2011-37835 and Examples thereof include the compounds described in Open 2012-173505.

The content of the acid diffusion control agent is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, and 0.05 to 0.05 parts by mass with respect to 100 parts by mass of the resist composition component. It is more preferably 3 parts by mass.

Examples of the organic carboxylic acid include aliphatic carboxylic acid, alicyclic carboxylic acid, unsaturated aliphatic carboxylic acid, oxycarboxylic acid, alkoxycarboxylic acid, ketocarboxylic acid, benzoic acid derivative, phthalic acid, terephthalic acid, isophthalic acid, 2 Examples thereof include −naphthoic acid, 1-hydroxy-2-naphthoic acid, 2-hydroxy-3-naphthoic acid and the like. When electron beam exposure is performed by vacuuming, it may volatilize from the surface of the resist film and contaminate the inside of the drawing chamber. Therefore, preferable organic carboxylic acids are aromatic organic carboxylic acids, among which, for example, benzoic acid. 1-Hydroxy-2-naphthoic acid and 2-hydroxy-3-naphthoic acid are preferable.

The content of the organic carboxylic acid is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and even more preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the resist composition component. Is.

Examples of the organic solvent include ethylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether. Acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl β-methoxyisobutyrate, ethyl butyrate, propyl butyrate, methylisobutylketone, ethyl acetate, isoamyl acetate, ethyl lactate, toluene, xylene, cyclohexyl acetate, diacetone Alcohol, N-methylpyrrolidone, N, N-dimethylformamide, γ-butyrolactone, N, N-dimethylacetamide, propylene carbonate, ethylene carbonate and the like are preferable. These organic solvents are used alone or in combination.

The resist composition component is preferably dissolved in the above solvent at a solid content concentration of 1 to 40% by mass. It is more preferably 1 to 30% by mass, still more preferably 3 to 20% by mass. The above film thickness can be achieved by setting the solid content concentration in the range.

When the resist composition of one embodiment of the present invention comprises a polymer, the polymer preferably has a weight average molecular weight of 2000 to 200,000, more preferably 2000 to 50000, and further preferably 2000 to 15000. preferable. The preferred dispersity (molecular weight distribution) (Mw / Mn) of the polymer is 1.0 to 1.7, more preferably 1.0 to 1.2, from the viewpoint of sensitivity. The weight average molecular weight and dispersity of the polymer are defined as polystyrene-equivalent values measured by GPC.

The composition of one aspect of the present invention is obtained by mixing each component of the above composition, and the mixing method is not particularly limited.

<3> Method for preparing resist composition The method for preparing the resist composition according to one aspect of the present invention is not particularly limited, and the resist composition is prepared by a known method such as mixing, dissolving or kneading the above polymer and other optional components. be able to.
The polymer can be synthesized by appropriately polymerizing the monomers constituting the units A and B, and if necessary, the monomers constituting the other units by a usual method. However, the method for producing a polymer according to the present invention is not limited to this.

<4> Device Manufacturing Method One embodiment of the present invention includes a step of forming a resist film on a substrate using the resist composition, and a step of exposing the resist film using particle beams or electromagnetic waves. This is a method for manufacturing a device, which includes a step of developing the exposed resist film to obtain a pattern.

Examples of the particle beam or electromagnetic wave used for exposure in the exposure step include electron beam and EUV, respectively.
The amount of light irradiation varies depending on the type and blending ratio of each component in the resist composition, the film thickness of the coating film, and the like, but is preferably 1 J / cm ² or less or 1000 μC / cm ² or less.
When the resist composition is contained in the polymer as a sensitizing unit (unit D) or as a sensitizing compound, it is secondly activated by ultraviolet rays or the like after irradiation with a first active energy ray such as a particle beam or an electromagnetic wave. It is also preferable to irradiate with energy rays.

One embodiment of the present invention comprises a step of forming a resist film, a step of irradiating a first active energy ray, a step of optionally irradiating a second active energy, and a step of forming a pattern using the above composition. It may be a method of manufacturing a substrate which includes and has a pattern before obtaining an individualized chip.
One embodiment of the present invention includes a step of forming a coating film on a substrate using the above composition, and exposing the coating film with a first active energy ray and optionally a second active energy ray to form an interlayer. It may be a method of manufacturing a device including a step of obtaining an insulating film.

The first active energy ray and the second active energy ray are not particularly limited as long as the onium salt structure according to some aspects of the present invention does not have significant absorption in the second active energy ray, but the first activity. When the energy ray is a particle beam, the second active energy ray is preferably an electromagnetic wave. When the first active energy ray is an electromagnetic wave, the wavelength of the first active energy ray is preferably shorter than the wavelength of the second active energy ray. Each active energy ray is illustrated below.
The first active energy ray is not particularly limited as long as an active species such as an acid can be generated in the resist film after irradiation with the resist film. For example, KrF excimer laser light, ArF excimer laser light, electron beam or extreme. Ultraviolet light (EUV) and the like are preferably mentioned.

As the second active energy ray, the acetal or thioacetal portion of the sensitizing compound of the above general formula (XI) or the unit D having the same is deprotected by the acid generated in the resist film after the irradiation with the first active energy ray. Any light may be used as long as it can activate the ketone derivative thus produced. For example, it means KrF excimer laser light, UV, visible light, etc., and it is particularly preferable to use light in the range of 365 nm (i line) to 436 nm (g line) among UV light.

The substrate is not particularly limited and a known substrate can be used. For example, a metal substrate such as silicon, silicon nitride, titanium, tantalum, palladium, copper, chromium, aluminum; a glass substrate; and the like can be mentioned.
In one embodiment of the present invention, the active energy rays used for exposure in the photolithography step used to obtain an interlayer insulating film for creating an LSI include UV, KrF excimer laser light, ArF excimer laser light, electron beams, or Extreme ultraviolet (EUV) and the like are preferably mentioned.

In one aspect of the present invention, the film thickness of the resist film formed by the resist composition is preferably 10 to 200 nm. The resist composition is applied onto a substrate by an appropriate coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc., and is applied at 60 to 150 ° C. for 1 to 20 minutes, preferably 80 to 80 to. Prebake at 120 ° C. for 1-10 minutes to form a thin film. The film thickness of this coating film is 5 to 200 nm, preferably 10 to 100 nm.

In one embodiment of the present invention, a film formed by the resist composition is formed at 60 to 150 ° C. for 1 to 20 minutes, preferably after the irradiation with the first active energy ray and between the irradiation with the second active energy ray. Post-bake at 80-120 ° C. for 1-10 minutes.
By performing post-baking, the cross-linking reaction between the acid bonded to the polymer generated after the irradiation with the first active energy ray and the unit B proceeds, and the cross-linking density of the polymer chain can be improved.

Hereinafter, some aspects of the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.
In the present invention, the molar extinction coefficient is at 365 nm in a chloroform solvent measured by a UV-VIS absorptiometer using chloroform as a solvent.
<Synthesis of compound A1 constituting unit A>
(Synthesis Example 1) Synthesis of dibenzothiophene-9-oxide

Dissolve 7.0 g of dibenzothiophene in 21.0 g of formic acid to bring it to 35 ° C. 4.1 g of 35 mass% hydrogen peroxide solution is added dropwise thereto, and the mixture is stirred at 25 ° C. for 5 hours. After cooling, the reaction solution is added dropwise to 50 g of pure water to precipitate a solid. The precipitated solid is separated by filtration, washed twice with 20 g of pure water, and then recrystallized with acetone. This is filtered and then dried to obtain 7.6 g of dibenzothiophene-9-oxide.

(Synthesis Example 2) Synthesis of 9-Phenyldibenzothiophenium-Methanesulfonate

7.0 g of dibenzothiophene-9-oxide and 2.7 g of benzene obtained in Synthesis Example 1 above are dissolved in 33 g of methanesulfonic acid to bring the temperature to 25 ° C. To this, 2.6 g of diphosphorus pentoxide is added, and the mixture is stirred at room temperature for 15 hours. Then, 105 g of pure water is added, the mixture is further stirred for 5 minutes, and then washed twice with 35 g of ethyl acetate to obtain 115 g of a 9-phenyldibenzothiophenium-methanesulfonate aqueous solution.

(Synthesis Example 3) Synthesis of 9-Phenyldibenzothiophenium-para-styrene sulfonate (Compound A1)

115 g of the 9-phenyldibenzothiophenium-methanesulfonate aqueous solution obtained in Synthesis Example 2, 5.8 g of para-styrenesulfonate and 220 g of methylene chloride are mixed and stirred at 25 ° C. for 3 hours. After stirring, the organic layer was recovered, washed 3 times with 100 g of pure water, the recovered organic layer was concentrated, and the obtained solid was dried to 9-phenyldibenzothiophenium-para-styrene sulfonate (Compound A1). ) Is obtained in an amount of 9.9 g. 365nm molar extinction coefficient of the resulting compound is less ^{1.0 × 10 5 cm 2 / mol} .

<Synthesis of compound A2 constituting unit A>
(Synthesis Example 4) Synthesis of 9-Phenyldibenzothiophenium-4-methacrylicoxy-1,1,2-trifluorobutanesulfonate (Compound A2)

9-Phenyldibenzothiophenium was performed in the same manner as in Synthesis Example 3 above except that sodium 4-methacryloxy-1,1,2-trifluorobutanesulfonate was used instead of sodium para-styrene sulfonate. Obtain 12 g of -4-methacryloxy-1,1,2-trifluorobutane sulfonate (Compound A2).

<Synthesis of compound A3 constituting unit A>
(Synthesis Example 5) Synthesis of 2,3,5,6-Tetrafluoro-4-Sodium Methacrylic Oxybenzene Sulfonate

Mix 17.5 g of sodium 2,3,5,6-tetrafluoro-4-hydroxybenzenesulfonate, 6.2 g of methacrylic acid, and 50 ml of tetrafluoroacetic acid, cool to 0 ° C., add 22 ml of trifluoroacetic anhydride, and add for 30 minutes. Stir. Then, the volatile components were distilled off with a rotary evaporator, and the obtained white solid was washed with 100 ml of acetone and then dried to obtain 21 g of sodium 2,3,5,6-tetrafluoro-4-methacryloxybenzenesulfonate. obtain.

(Synthesis Example 6) Synthesis of 9-Phenyldibenzothiophenium-2,3,5,6-tetrafluoro-4-methacrylicoxybenzenesulfonate (Compound A3)

9-Phenyldibenzothio by performing the same operation as in Synthesis Example 3 above except that sodium 2,3,5,6-tetrafluoro-4-methacryloxybenzenesulfonate is used instead of sodium para-styrene sulfonate. Obtain 12.8 g of phenyloxy-2,3,5,6-tetrafluoro-4-methacryloxybenzenesulfonate (Compound A3).

(Synthesis Example 7) Triphenylsulfonium-methanesulfonate

115 g of a triphenylsulfonium-methanesulfonate aqueous solution can be obtained by performing the same operation as in Synthesis Example 2 above except that diphenylsulfoxide is used instead of dibenzothiophene-9-oxide.

<Synthesis of compound A4 constituting unit A>
(Synthesis Example 8) Synthesis of N-methacryl-N-methylaminoethanesulfonic acid

Add 3.6 g of methacrylic acid and 32.5 g of diisopropylethylamine to 752 g of dichloromethane, cool to −30 ° C., add 13.7 g of diethyl cyanophosphate, and stir. After 20 minutes, the temperature is raised to −20 ° C., and 47 g of a dichloromethane solution of 4.9 g of N-methylaminoethanesulfonic acid is added. Two hours later, 252 g of a 1N hydrochloric acid aqueous solution was added, the organic layer was recovered, and the composition obtained by concentration was purified by column chromatography to obtain 5.8 g of N-methacryl-N-methylaminoethanesulfonic acid. ..

(Synthesis Example 9) Synthesis of triphenylsulfonium-N-methacryl-N-methylaminoethanesulfonate (Compound A4)

After dissolving 5.8 g of N-methacryl-N-methylaminoethanesulfonic acid obtained in Synthesis Example 8 and 1.1 g of sodium hydroxide in 30 g of pure water, the triphenylsulfonium-methane obtained in Synthesis Example 7 above was dissolved. Add 125 g of sulfonate aqueous solution and 220 g of dichloromethane and stir for 3 hours. Then, the organic layer was recovered, washed 3 times with 100 g of pure water, the recovered organic layer was concentrated, and the obtained solid was dried to 9-phenyldibenzothiophenium-N-methacryl-N-methylamino. Obtain 11 g of ethane sulfonate (Compound A4).

<Synthesis of compound A5 constituting unit A>
(Synthesis Example 10) Synthesis of triphenylsulfonium-4-vinylbenzoate (Compound A5)

By performing the same operation as in Synthesis Example 9 above except that 4-vinylbenzoic acid is used instead of N-methacryl-N-methylaminoethanesulfonic acid, triphenylsulfonium-4-vinylbenzoate (Compound A5) is 2 Obtain 0.8 g.

(Synthesis Example 11) Synthesis of 1- (4-methoxynaphthalene-1-yl) tetrahydrothiophenium-methanesulfonate

By performing the same operation as in Synthesis Example 2 above except that tetramethylene sulfoxide is used instead of dibenzothiophene-9-oxide and 1-methoxynaphthalene is used instead of benzene, 1- (4-methoxynaphthalene-1-) is used. Il) Obtain 114 g of a tetrahydrothiophenium-methanesulfonate aqueous solution.

<Synthesis of compound A6 constituting unit A>
(Synthesis Example 12) Synthesis of 2,6-difluoro-4-vinylbenzoic acid

8.3 g of 4-vinyl-2,6-difluoro-benzoic acid and 8.4 g of magnesium sulfate, 4.2 g of 2,4,6-trivinylcyclotriboroxane-pyridine complex, 0.44 g of tetrakistriphenylphosphine palladium, 7.0 g of calcium carbonate is dissolved in 150 g of pure water and 477 g of 1,2-dimethoxyethane, and the mixture is refluxed for 20 hours. Then, 500 g of ethyl acetate was added and the recovered organic layer was concentrated and purified by column chromatography to obtain 5.2 g of 2,6-difluoro-4-vinylbenzoic acid.

(Synthesis Example 13) Synthesis of 1- (4-methoxynaphthalene-1-yl) tetrahydrothiophenium-2,6-difluoro-4-vinylbenzoate (Compound A6)

Except for the use of 2,6-difluoro-4-vinylbenzoic acid in place of N-methacryl-N-methylaminoethanesulfonic acid and 5-naphthyltetramethylenesulfonium-methanesulfonate in place of triphenylsulfonium-methanesulfonate. By performing the same operation as in Synthesis Example 9, 4.4 g of 1- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium-2,6-difluoro-4-vinylbenzoate (Compound A6) is obtained.

<Synthesis of compound A7 constituting unit A>
(Synthesis Example 14) Synthesis of 1-methacryl-4-piperidin carboxylate methyl

By performing the same operation as in Synthesis Example 8 above except that methyl 4-piperidinecarboxylate is used instead of N-methylethanesulfonic acid, 5.9 g of methyl 1-methacryl-4-piperidine carboxylate can be obtained.

(Synthesis Example 15) Synthesis of triphenylsulfonium-1-methacryl-4-piperidincarboxylate (Compound A7)

Methyl 1-methacryl-4-piperidincarboxylate was used in place of N-methacryl-N-methylaminoethanesulfonic acid, and the mixture was heated at 70 ° C. for 1 hour to cool to 25 ° C. after hydrolysis, and then triphenylsulfonium-. 2.3 g of triphenylsulfonium-1-methacryl-4-piperidincarboxylate (Compound A7) is obtained by performing the same operation as in Synthesis Example 9 except that methanesulfonate is added.

<Synthesis of compound A8 constituting unit A>
(Synthesis Example 16) Synthesis of dibenzothiophen-2-yl-dibenzothiophenium-methanesulfonate

118 g of an aqueous solution of dibenzothiophene-2-yl-dibenzothiophenium-methanesulfonate can be obtained by performing the same operation as in Synthesis Example 2 except that dibenzothiophene is used instead of benzene.

(Synthesis Example 17) Synthesis of 2,2,3,3,4,4-hexafluoro-4- (4-vinylbenzoyl) butanoic acid

7.1 g of 4-bromostyrene is dissolved in 32 g of tetrahydrofuran, and 39 ml of a THF solution of 1 mol / L methylmagnesium bromide is added dropwise thereto at 5 ° C. or lower. After the dropwise addition, the mixture is stirred at 5 ° C. or lower for 30 minutes to obtain a THF solution of 4-vinylphenylmagnesium bromide. A THF solution of 4-methylthiophenylmagnesium bromide was added dropwise at 10 ° C. or lower in a solution prepared by dissolving 9.5 g of 2,2,3,3,4,4-hexafluoropentanediic anhydride in 15 g of THF, and then 25. Stir at ° C. for 1 hour. After stirring, 50 g of a 10 mass% ammonium chloride aqueous solution is added at 20 ° C. or lower, and the mixture is further stirred for 10 minutes, and the organic layer is extracted with 80 g of ethyl acetate. The solid obtained by washing this with water and distilling off ethyl acetate and tetrahydrofuran was purified by column chromatography to obtain 2,2,3,3,4,5-hexafluoro-4- (4-vinylbenzoyl). ) Obtain 9.1 g of butanoic acid.

(Synthesis Example 18) Synthesis of dibenzothiophen-2-yl-dibenzothiophenium-2,2,3,3,4,5-hexafluoro-4- (4-vinylbenzoyl) butanate (Compound A8)

Use 2,2,3,3,4,4-hexafluoro-4- (4-vinylbenzoyl) butanoic acid instead of N-methacryl-N-methylaminoethanesulfonic acid and replace triphenylsulfonium-methanesulfonate. 9- (2-Dibenzothiophenyl) dibenzothiophenium-2,2, by performing the same operation as in Synthesis Example 9 above except that dibenzothiophene-2-yl-dibenzothiophenium-methanesulfonate is used. Obtain 11.6 g of 3,3,4,4-hexafluoro-4- (4-vinylbenzoyl) butanate (Compound A8).

<Synthesis of compound A9 constituting unit A>
(Synthesis Example 19) Synthesis of bis (4-tert-butylbenzene) iodonium-4-methacrylicoxy-1,1,2-trifluorobutanesulfonate (Compound A9)

To 36 g of sulfuric acid, 9.1 g of 1-iodo-4-tert-butylbenzene is added, and then 35 g of potassium persulfate is added little by little at 10 ° C. or lower, and the mixture is stirred for 30 minutes. After stirring, 62.8 g of t-butylbenzene is added and the mixture is further stirred at 25 ° C. for 3 hours. After stirring, 68.2 g of pure water was added at 10 ° C. or lower, 90 g of methylene chloride and 11.5 g of sodium 4-methacryloyloxy-1,1,2-trifluorobutanesulfonate were added, and the temperature was 25 ° C. for 2 hours. Stir to some extent. This is separated and washed with water three times, and then methylene chloride is distilled off to obtain a crude product. By purifying the crude product by silica gel column chromatography (methylene chloride / methanol = 90/10 (volume ratio)), bis (4-tert-butylbenzene) iodonium-4-methacryloxy-1,1,2-trifluoro Obtain 18.7 g of butane sulfonate (Compound A9).

<Synthesis of compound A10 constituting unit A>
(Synthesis Example 20) Synthesis of 4-bromo-4'-phenylsulfanylbenzophenone

3.0 g of aluminum chloride is added to 28 g of methylene chloride to bring the temperature to 0 ° C. After adding 4.0 g of diphenyl sulfide to this, 3.4 g of 4-bromobenzoyl chloride is dissolved in 6.8 g of methylene chloride and added dropwise over 30 minutes. After the dropping, the mixture is stirred at 25 ° C. for 1 hour, 60 g of pure water is added, the mixture is further stirred for 5 minutes, and then washed twice with 20 g of toluene. This is separated and the obtained organic layer is distilled off with a solvent. The obtained residue is purified by recrystallization using 30 g of isopropyl alcohol to obtain 5.2 g of 4-bromo-4'-phenylsulfanylbenzophenone.

(Synthesis Example 21) Synthesis of 4-bromo-4'-phenylsulfanylbenzophenone dimethyl acetal

5.0 g of 4-bromo-4'-phenylsulfanylbenzophenone obtained in Synthesis Example 20 was dissolved in 30 g of methanol, 5.0 g of trimethyl orthoformate and 30 mg of concentrated sulfuric acid were added thereto, and the mixture was stirred at 60 ° C. for 4 hours. To do. After stirring, 150 g of 3% by mass aqueous sodium hydrogen carbonate is added, and the mixture is further stirred for 10 minutes to precipitate a solid. The precipitated solid is filtered off and redissolved in 30 g of methylene chloride. After washing this with water three times, methylene chloride is distilled off to obtain 5.0 g of 4-bromo-4'-phenylsulfanylbenzophenone dimethyl acetal.

(Synthesis Example 22) Synthesis of {4- [dimethoxy- (4-phenylsulfanylphenyl) methyl] phenyl} diphenylsulfonium-para-styrenesulfonate (Compound A10)

To activate the magnesium, 2.0 g of tetrahydrofuran, 0.4 g of magnesium and 1,2-dibromoethane are added to the pre-dried flask. After confirming the activation, the temperature of the solution was raised to 50 ° C., and 4.0 g of 4-bromo-4'-phenylsulfanylbenzophenone dimethyl acetal obtained in Synthesis Example 20 was dissolved in 6.0 g of THF. Is dropped. After the dropwise addition, the mixture is stirred at 50 ° C. for 5 hours to obtain a THF solution of 4- [dimethoxy- (4-phenylsulfanylphenyl) methyl] phenylmagnesium bromide. A THF solution of 4- [dimethoxy- (4-phenylsulfanylphenyl) methyl] phenylmagnesium bromide was added to a solution of 1.9 g of diphenylsulfoxide, 1.8 g of trimethylsilyl chloride and 0.8 g of triethylamine in 9.5 g of methylene chloride. The mixture is added dropwise at 10 ° C. or lower, and then stirred at 25 ° C. for 1 hour. After stirring, 30 g of a 10 mass% ammonium chloride aqueous solution is added at 5 ° C. or lower, the mixture is further stirred for 10 minutes, and washed twice with 5.0 g of isopropyl ether. Then, 40 g of methylene chloride and 2.2 g of sodium para-styrene sulfonate are added, and the mixture is stirred at 25 ° C. for about 2 hours. Crude crystals are obtained by separating the liquid, washing with water three times, and then distilling off methylene chloride. By purifying the crude crystals by silica gel column chromatography (methylene chloride / methanol = 90/10 (volume ratio)), {4- [dimethoxy- (4-phenylsulfanylphenyl) methyl] phenyl} diphenylsulfonium-para-styrene sulfonate Obtain 5.4 g of (Compound A10). 365nm molar extinction coefficient of the resulting compound is less ^{1.0 × 10 5 cm 2 / mol} .

(Synthesis Example 23) Synthesis of [4- (4-phenylsulfanylbenzoyl) phenyl] diphenylsulfonium-para-styrenesulfonate (Compound A11)

2.0 g of {4- [dimethoxy- (4-phenylsulfanylphenyl) methyl] phenyl} diphenylsulfonium-para-styrenesulfonate obtained in Synthesis Example 22 is dissolved in 20 g of methanol. 0.05 g of methanesulfonic acid is added to this solution, and the mixture is stirred at 30 ° C. for 2 hours. After stirring, 0.1 g of triethylamine is added, and then methanol is distilled off. Purify the obtained crude crystals by silica gel column chromatography) to obtain 1.3 g of [4- (4-phenylsulfanylbenzoyl) phenyl] diphenylsulfonium-para-styrenesulfonate (Compound A11). The 365 nm molar extinction coefficient of the obtained compound is 7.0 × 10 ⁶ cm ² / mol.

<Synthesis of compound B1 constituting unit B>
(Synthesis Example 23) Synthesis of 4-vinylphenyl-triphenyltin (Compound B1)

Add 1.2 g of magnesium and 6 g of THF to the flask from which water has been removed in advance. A solution prepared by dissolving 6.0 g of 4-vinylbromobenzene in 12.0 g of THF is added dropwise thereto over 1 hour. After stirring for 1 hour after the dropping, the obtained 4-vinylphenylmagnesium bromide solution is added dropwise to a flask containing 7.3 g of triphenyltin chloride and 36 g of THF prepared separately over 30 minutes at 5 ° C. After the dropping, the mixture is stirred for 30 minutes, 600 g of a 1% aqueous ammonium chloride solution is added, and the mixture is further stirred for 10 minutes. Then, THF is distilled off and extraction is performed with 60 g of toluene. This is separated and the obtained organic layer is washed 3 times with 60 g of pure water. Then, the organic layer obtained by separating the liquids was distilled off from the solvent and then purified by column chromatography (ethyl acetate / hexane = 5/95 (volume ratio)) to 4-vinylphenyl-triphenyltin (compound). Obtain 5.6 g of B1).

<Synthesis of compound B2 constituting unit B>
(Synthesis Example 24) Synthesis of 4-isopropenylphenyl-triphenyltin (Compound B2)

7.1 g of 4-isopropenylphenyl-triphenyltin (Compound B2) can be obtained by carrying out the same operation as in Synthesis Example 23 except that 4-isopropenylbromobenzene is used instead of 4-vinylbromobenzene.

<Synthesis of compound B3 constituting unit B>
(Synthesis Example 25) Synthesis of 4-vinylphenyl-tributyltin (Compound B3)

5.1 g of 4-vinylphenyl-tributyltin (Compound B3) can be obtained by performing the same operation as in Synthesis Example 23 except that tributyltin chloride is used instead of triphenyltin chloride.

<Synthesis of compound B4 constituting unit B>
(Synthesis Example 26) Synthesis of 4-vinylphenyl-triphenylgerman (Compound B4)

3.1 g of 4-vinylphenyl-tributyl germanium (Compound B4) can be obtained by performing the same operation as in Synthesis Example 23 except that triphenylgermanium chloride is used instead of triphenyltin chloride.

<Synthesis of compound B5 constituting unit B>
(Synthesis Example 27) Synthesis of Phenyl-4-styrenyl terlide (Compound B5)

8.6 g of phenyl-4-styrenyl terlide (Compound B5) can be obtained by carrying out the same operation as in Synthesis Example 23 except that diphenyl deterlide is used instead of triphenyltin chloride.

<Synthesis of compounds constituting unit D1>
(Synthesis Example 28) Synthesis of 4- (2-vinyloxy) ethylthiobromobenzene

5.0 g of 4-bromothiophenol, 5.7 g of chloroethyl vinyl ether and 7.3 g of potassium carbonate were dissolved in 20 g of acetone and stirred at the reflux temperature for 3 hours. Then, the mixture was cooled to room temperature, 60 g of pure water was added, and the mixture was stirred for 5 minutes. To this was added 90 g of toluene, extracted, and washed separately with water. Then, toluene is distilled off to obtain 6.4 g of 4- (2-vinyloxy) ethylthiobromobenzene.

(Synthesis Example 29) Synthesis of 4- (2-vinyloxy) ethylthio-2', 4'-dimethoxybenzophenone

10.2 g of 4- (2-vinyloxy) ethylthiobromobenzene is dissolved in 32 g of tetrahydrofuran, and 39 ml of a THF solution of 1 mol / L methylmagnesium bromide is added dropwise thereto at 5 ° C. or lower. After the dropwise addition, the mixture is stirred at 5 ° C. or lower for 30 minutes to obtain a THF solution of 4-methylthiophenylmagnesium bromide. A THF solution of 4-methylthiophenylmagnesium bromide is added dropwise to a solution of 8.8 g of 2,4-dimethoxybenzoyl chloride in 15 g of THF at 10 ° C. or lower, and then the mixture is stirred at 25 ° C. for 1 hour. After stirring, 50 g of a 10 mass% ammonium chloride aqueous solution is added at 20 ° C. or lower, and the mixture is further stirred for 10 minutes, and the organic layer is extracted with 80 g of ethyl acetate. After washing this with water, ethyl acetate and tetrahydrofuran are distilled off to obtain crude crystals. The crude crystals are recrystallized from 120 g of ethanol to obtain 8.4 g of 4- (2-vinyloxy) ethylthio-2', 4'-dimethoxybenzophenone).

(Synthesis Example 30) Synthesis of 4- (2-hydroxy) ethylthio-2', 4'-dimethoxybenzophenone

Add 5.0 g of 4- (2-vinyloxy) ethylthio-2', 4'-dimethoxybenzophenone, 3.3 g of pure water and 0.44 g of pyridinium-p-toluenesulfonic acid to 30 g of acetone at reflux temperature. The mixture was stirred for 3 hours. Then, the mixture was cooled to room temperature, 85 g of pure water was added, the mixture was stirred for 5 minutes, and then extracted with ethyl acetate. This is separated and washed with water, and then ethyl acetate is distilled off to obtain 4.6 g of 4- (2-hydroxy) ethylthio-2', 4'-dimethoxybenzophenone.

(Synthesis Example 31) Synthesis of 4- (2-methacrylicoxy) ethylthio-2', 4'-dimethoxybenzophenone

5 g of 4- (2-hydroxy) ethylthio-2', 4'-dimethoxybenzophenone and 2.9 g of methacrylic anhydride are dissolved in 15 g of THF, and 1.9 g of triethylamine is added dropwise thereto at 20 ° C. or lower in 30 minutes. To do. After the dropping, the mixture is stirred at 25 ° C. for 3 hours, 40 g of pure water is added, and the mixture is further stirred for 10 minutes. This is extracted with 50 g of ethyl acetate and washed separately with pure water. Then, ethyl acetate is distilled off to obtain 5.1 g of the desired 4- (2-methacrylicoxy) ethylthio-2', 4'-dimethoxybenzophenone. The 365 nm molar extinction coefficient of the obtained compound is 1.1 × 10 ⁶ cm ² / mol.

(Synthesis Example 32) Synthesis of 4-[(2-methacrylicoxy) ethylthio] -phenyl- (2', 4'-dimethoxyphenyl) dimethoxymethane (Compound D1)

Dissolve 6.7 g of 4- (2-methacryloxy) ethylthio-2', 4'-dimethoxybenzophenone, 47 mg of sulfuric acid and 13.5 g of trimethyl orthoformate in 12.5 g of methanol, and stir this at reflux temperature for 3 hours. .. Then, the mixture is cooled to room temperature, 50 g of a 5 mass% aqueous sodium hydrogen carbonate solution is added thereto, the mixture is further stirred for 10 minutes, and the precipitated crystals are filtered. The crystals are collected, redissolved in 50 g of ethyl acetate, and then washed with water. Then, by distilling off ethyl acetate, 2.6 g of 4-[(2-methacrylicoxy) ethylthio] -phenyl- (2', 4'-dimethoxyphenyl) dimethoxymethane (Compound D) is obtained.
365nm molar extinction coefficient of the resulting compound is less ^{1.0 × 10 5 cm 2 / mol} .

<Synthesis of Polymer 1>
(Synthesis Example 33) Synthesis of Polymer 1

3.6 g of compound A1 constituting unit A, 5.3 g of compound B1 constituting unit B, and 0.31 g of dimethyl-2,2'-azobis (2-methylpropionate) as a polymerization initiator. 0.06 g of 2-mercaptoethanol is dissolved in a mixed solution of 9 g of methanol, 9 g of γ-butyrolactone and 9 g of cyclohexanone to deoxidize. This is added dropwise to a mixed solution of 3 g of methanol previously heated to 70 ° C., 3 g of γ-butyrolactone and 3 g of cyclohexanone over 4 hours. After dropping, the mixture is stirred for 2 hours and then cooled. After cooling, it is reprecipitated by dropping it on 90 g of diisopropyl ether. This is filtered and vacuum dried to obtain 5.4 g of the target polymer 1.
Although the unit ratio of the polymer is disclosed above, the polymer of some embodiments of the present invention is not limited thereto.

<Synthesis of polymers 2-28>
(Synthesis Example 34) Synthesis of Polymers 2-28 Following Synthesis Example 33, the compounds A1 to A6 constituting unit A, the compounds B1 to B5 constituting unit B, and the monomers C1 to C5 constituting unit C, Polymers 2 to 28 were synthesized from the compound D1 constituting the unit D, the monomers E1 constituting the unit E, the monomers F1 to F3 constituting the unit F, and the monomers G1 having low reactivity to the acid. Monomers C1 to C2, monomers F1 and F3 were purchased products, and monomers E1 and F2 and monomer G1 were synthesized by esterifying an alcohol compound as a precursor of the compound according to the above publications and documents. The structure is shown below.
The details of each synthesized polymer are shown in Table 1.
Monomer C1: 4-tert-Butoxystyrene Monomer C2: 1-ethoxyethoxymethacrylate Monomer E1: 2-Hydroxypinanyl-3-parastyrene Styrene Monomer F1: α-methacryloxy-γ-butyrolactone monomer F2: 2-methacryloyloxy- 1,3-Propane Styrene Monomer F3: 3-Hydroxyadamantan-1-methacrylate Monomer G1: Triphenyl- (4-methacryloxyphenyl) methane additive A: (4-methylthio) phenyl- (4'-phenylthio) phenyl- Dimethoxymethane

<Preparation of resist composition>
(Sample preparation of Examples 1 to 6 and Comparative Example 1)
400 mg of any of the above polymers is dissolved in a mixed solvent of 4 ml of γ-butyrolactone and 4 ml of cyclohexanone to prepare resist composition samples of Examples 1 to 6 and Comparative Example 1. For the sample of Example 5, 45 mg of Additive A is further added as a sensitizing compound. The sample configurations are shown in Tables 2 and 3.

(Adjustment of sample of Comparative Example 2)
350 mg of p-hydroxystyrene (molecular weight 8000), 30 mg of 1,3,4,6-tetrakis (methoxymethyl) glycoluryl as a cross-linking agent, 20 mg of triphenylsulfonium-nonafluorosulfonate as an acid generator, and trioctyl as an acid diffusion control agent. Sample 5 shown in Comparative Example 2 is prepared by dissolving 1.5 mg of amine in 8 ml of cyclohexanone.

<Preparation of developer>
Of the above polymers 1 to 28, pure water, methanol, tetrahydrofuran (THF), and acetonitrile (so that each polymer is dissolved in 15% by mass with respect to the polymers 1, 2, 11, 13, 18 and 28 used in the sensitivity evaluation). AN) and methyl ethyl ketone (MEK) are blended so that the composition is in the range of 0 to 90% by volume, respectively, and a developing solution suitable for each polymer is prepared. The results of polymers 1, 2, 11, 13, 18 and 28 are shown in Table 2.

<Evaluation of electron beam sensitivity>
Sample 1 of the resist composition is spin-coated on a silicon wafer previously modified with hexamethylene disilazane. This is prebaked on a hot plate at 110 ° C. for 1 minute to obtain a substrate on which a coating film having a thickness of 200 nm is formed. An electron beam drawing device is used to draw on the coating film of the substrate with an electron beam of 30 keV so as to form a line and space pattern of 2 μm. The substrate after electron beam irradiation is post-baked on a hot plate at 130 ° C. for 5 minutes, developed with the above developer for 1 minute, and then rinsed with pure water to obtain a line-and-space pattern of 2 μm. The irradiation amount at this time is set to E _max [μC / cm ² ], and the sensitivity by electron beam irradiation is obtained. In addition, the shape of the obtained pattern is observed to evaluate whether or not a rectangular pattern is obtained. The case where a rectangular pattern is obtained is evaluated as ◯, the case where a tapered pattern shape is obtained is evaluated as Δ, and the case where a pattern cannot be obtained is evaluated as ×.
The sensitivities of Samples 2 to 4 in Examples 1 to 3 and Comparative Example 1 were evaluated in the same manner as above, and only Sample 5 in Comparative Example 2 was a 2.38 mass% tetramethylammonium hydroxide aqueous solution (TMAH). ) Is used for development to evaluate the sensitivity.
The results are shown in Table 3. In Table 3, the sensitivity of Example 1 is set to 100, and the evaluation results of the samples (Examples 2 and 3 and Comparative Examples 1 and 2) are calculated as relative values.

In Examples 1 to 3 of Table 3, by heating after electron beam irradiation, the solubility is changed by the cross-linking reaction between the produced polymer acid and the unit B, and a pattern can be obtained. On the other hand, in the case of Comparative Example 1 in which the unit G having no metal atom is used instead of the unit B, patterning cannot be performed even if the irradiation is performed 5 times or more as in Example 1. This is because the unit B undergoes a cross-linking reaction with the polymer-type conjugate base due to heating, which causes a dissolution contrast between the exposed part and the unexposed part, and the unit B is important in the polymer for constructing the crosslinked structure. It can be seen that it is.

From the comparison between Example 1 and Comparative Example 2 in Table 3, it can be seen that the result of Example 1 is superior to Comparative Example 2 in sensitivity and pattern shape. In Example 1, the efficiency of secondary electron generation by electron beam irradiation is improved by introducing the unit B having a structure containing metal atoms or antimetal atoms (structure containing tin atoms). As a result, the decomposition efficiency of the unit A increases. Therefore, the sensitivity is higher than that of Comparative Example 2 using the catalytic reaction of a slight acid generated by electron beam irradiation, and by uniformly dispersing units A and B in the polymer by polymerization, the polymer acid is uniformly dispersed in the membrane. It can be said that the pattern shape is improved because it is generated. Since the tin atom contained in the unit B is also an atom having high EUV absorption, the same effect can be expected in EUV.

From the comparison between Example 1 and Example 2, a flexible fluoroalkyl group is provided as a spacer structure between the polymer main chain and the acid structure like the compound A2 introduced into the polymer 2 of Example 2 after exposure. The molecular movement is caused by heating, and the cross-linking reaction is more likely to occur and the compound A1 having a phenylene group as a spacer structure is more rigid than the polymer 1 of Example 1. The spacer structure corresponds to the L ¹ and R ² portions of the above general formulas (1) and (2).

From the comparison between Example 1 and Example 3, the polymer acid of the carboxylic acid generated by deprotection by the polymer acid generated from the unit A by introducing the unit C, which is the acid dissociative group unit of Example 3, is exposed. Subsequent heating causes a cross-linking reaction with unit B. As a result, the crosslink density is improved and the sensitivity is superior. Since unit B is reactive with acid, even if a unit that produces polymer acid by an acid catalyst such as unit C is introduced, the acid can be competitively inactivated, so an acid diffusion control agent or the like is added. The pattern can be formed without doing anything.

<Light sensitization evaluation>
Samples 6 to 8 were drawn with an electron beam so as to have a line-and-space pattern of 2 μm after spin coating in the same manner as in the electron beam evaluation, and then the wafer taken out was exposed to a wavelength of 365 nm using a bandpass fifilter. Using a black light (FL8BL, manufactured by Hitachi Appliances, Inc.) adjusted to ± 5 nm, the entire surface of the wafer is irradiated with 500 mJ / cm ² . The substrate after UV irradiation is post-baked on a hot plate at 130 ° C. for 5 minutes, then developed with the above developer for 1 minute, and then rinsed with pure water to obtain a line-and-space pattern of 2 μm. The irradiation amount at this time is set to E _max [μC / cm ² ], and the sensitivity by electron beam irradiation is obtained. The results are shown in Table 4. In Table 4, the sensitivity of Example 1 in Table 3 was set to 100, and the evaluation result of the sample with respect to the sensitivity was calculated as a relative value.

Table 4 from comparison between Example 4-7, since the polymer 1 that does not produce a compound with photosensitivity to 365nm by acid catalyzed reaction is the molar extinction coefficient of 365nm small as 1.0 × ¹⁰ 5 ^cm 2 / mol or less , No increase in sensitivity was observed by light irradiation. On the other hand, when compound A10, which becomes compound A11 by acid-catalyzed reaction, compound D1 and additive A, which absorbs 365 nm more by acid-catalyzed reaction, are added to the polymer as unit A, acid is generated by absorbing light of 365 nm. By acting as a sensitizer or acting as a sensitizer, the sensitivity can be increased by promoting the acid generation of the unit A.

According to some aspects of the present invention, it is possible to provide a polymer having high absorption efficiency of particle beams such as EUV or electromagnetic waves and excellent characteristics of sensitivity, resolution and pattern performance, and a resist composition containing the polymer.

Claims (12)

A polymer containing unit A and unit B.
The unit A has an onium salt structure having an anion portion and a cation portion, and is a unit that generates a state in which a polymer-type conjugated base and a hydrogen cation are paired by irradiation with a particle beam or an electromagnetic wave. The salt structure is covalently attached to the polymer backbone, either directly or via the first spacer.
The unit A is a polymer having a structure represented by the following general formula (1).

(In the general formula (1), R ¹ is any one selected from the group consisting of a hydrogen atom; a fluorine atom; and a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; ^The alkyl group in ¹ may have a substituent and may have a substituent.
R ² is selected from the group consisting of a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms; an arylene group having 6 to 14 carbon atoms; and a heteroarylene group having 4 to 14 carbon atoms. is either an alkylene group in R ^2, an arylene group and heteroarylene group may have a substituent,
L ¹ is a direct bond; carbonyloxy group; carbonylamino group; linear, branched or cyclic alkylenecarbonyloxy group; linear, branched or cyclic alkylenecarbonylamino group; arylenecarbonyloxy group; and arylenecarbonylamino group; is any one selected from the group consisting of an amino group in L ^1, an alkylene group and arylene group may have a substituent,
When a carbon-carbon single bond is contained in R ¹ , R ² and L ¹ , at least one of the carbon-carbon single bonds may be substituted with a carbon-carbon double bond or a carbon-carbon triple bond.
When a methylene group is contained in R ¹ , R ² and L ¹ , at least one of the methylene groups may be substituted with a divalent heteroatom-containing group.
M ⁺ is a sulfonium cation represented by the following general formula (3) or an iodonium cation represented by the following general formula (4). )
(In the general formulas (3) and (4), R ^{3 to} R ⁵ are independently linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms; aryl groups having 6 to 14 carbon atoms; Any of the group consisting of heteroaryl groups having 4 to 14 carbon atoms; the alkyl group, the aryl group and the heteroaryl group may have a substituent.
When a carbon-carbon single bond is contained in R ^{3 to} R ⁵ , at least one of the carbon-carbon single bonds may be replaced with a carbon-carbon double bond or a carbon-carbon triple bond.
When a methylene group is contained in R ^{3 to} R ⁵ , at least one of the methylene groups may be substituted with a divalent heteroatom-containing group.
The alkyl group, the aryl group and the heteroaryl group are bonded to R ³ and R ⁴ directly by a single bond or via any one selected from the group consisting of an oxygen atom, a sulfur atom and a methylene group. A ring structure may be formed together with a sulfonium cation or an iodonium cation. )
The unit B has a structure containing a metal atom or a metalloid atom, and the structure of the unit B is covalently bonded to the polymer main chain either directly or via a second spacer.
The polymer-type conjugate base is added or substituted with the metal atom or metalloid atom to form an acid ester structure.
A polymer in which the unit B has a structure represented by the following general formula (5).
(In the general formula (5), R ¹ , R ² and L ¹ are independently selected from the same options as R ¹ , R ² and L ^{1 in the} general formula (1) .
R ⁶ is selected from the same options as R ^{5 in the} general formula (3) .
X is the metal atom or metalloid atom,
In the general formula (5), two or more of R ² and a plurality of R ⁶ is a direct single bond, or, through any one selected from the group consisting of methylene group, the R ² and may form an X with ring structure more two coupling among the plurality of R ^6, h is a and 0-3 a valence -1 of X. ) The polymer according to claim 1, wherein the metal atom or metalloid atom is at least one atom selected from the group consisting of Si, As, Se, Ge, Sn, Sb, Te, Pb, Bi and Po . X is, Sn, Sb, Ge, polymer according to claim 1 or 2 is any atom selected from the group consisting of Bi and Te in the formula (5). The polymer according to any one of claims 1 to 3 , further containing unit C, wherein the unit C has any of the structures represented by the following general formulas (8) to (11).
^(R 1, ^{R 2} and ^{L 1} in the general formula (8) to (11) is selected from the same options as ^R 1, ^{R 2} and ^{L 1} in the general formula (1),
R ⁷ is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent.
R ⁸ and R ⁹ are linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms, which may independently have substituents, respectively.
Wherein two or more of R ^7, R ⁸ and R ⁹ are the direct bond or via any one selected from the group consisting of methylene group, it may form a ring structure,
R ¹⁰ is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent.
R ¹¹ and R ¹² are each independently selected from the group consisting of a hydrogen atom; and a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent. ,
Two or more of the R ¹⁰ , R ¹¹ and R ¹² may form a ring structure either directly in a single bond or via one selected from the group consisting of methylene groups.
Each R ¹³ is independently selected from the group consisting of an alkyl group; a hydroxy group; an alkoxy group; an alkylcarbonyl group; an alkylsulfanyl group; an alkylsulfinyl group; an alkylsulfonyl group; an amino group; a cyano group; a nitro group; and a halogen atom; is either being an alkyl group in R ^13, alkoxy groups, alkylcarbonyl group, an alkylsulfanyl group, alkylsulfinyl group and alkylsulfonyl group may have a substituent,
When a carbon-carbon single bond is present in R ^{7 to} R ¹³ , at least one of the carbon-carbon single bonds may be replaced with a carbon-carbon double bond or a carbon-carbon triple bond.
When a methylene group is contained in R ^{7 to} R ¹³ , at least one of the methylene groups may be substituted with a divalent heteroatom-containing group.
l ¹ is an integer of ¹ to 2, m ¹ is an integer of 0 to 4 when l ¹ is 1, and an integer of 0 to 6 when l ¹ is 2.
n ¹ is 1-5 when ^{l 1} is 1, and 1-7 integer when ^{l 1} is 2,
m ¹ + n ¹ is 1 to 5 when l ¹ is 1, and ¹ to 7 when l ¹ is 2. ) Further comprises a unit D, wherein unit D is claim 1 is a structure in which a compound represented by the following general formula (12) to (14) is bonded to the R ² group of the following general formula (15) 4 The polymer according to any one of the above.
(In the general formulas (12) to (14),
R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently selected from the group consisting of a hydrogen atom; an electron donating group; and an electron attracting group;
At least one of R ¹⁴ and R ¹⁵ is the electron donating group.
At least one of R ¹⁶ is the electron donating group.
R ¹⁷ is any one selected from the group consisting of a hydrogen atom; and a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms which may have a substituent.
R ¹⁸ is any of 2 independently selected from the group consisting of a hydrogen atom; and a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms which may have a substituent. One of R ¹⁸ may be bonded to form a ring structure,
When a carbon-carbon single bond is contained in R ^{14 to} R ¹⁸ , at least one of the carbon-carbon single bonds may be replaced with a carbon-carbon double bond or a carbon-carbon triple bond.
When a methylene group is contained in R ^{14 to} R ¹⁸ , at least one of the methylene groups may be substituted with a divalent heteroatom-containing group.
E is any of the group consisting of direct bonds, oxygen atoms; sulfur atoms and methylene groups.
m ³ is an integer of 0 or 1 and
n ⁵ and n ⁶ are integers from 0 to 2, respectively, and n ⁵ + n ⁶ is 2.
When n ⁵ is 1, n ³ is an integer from 0 to 4, when n ⁵ is 2, n ³ is an integer from 0 to 6, and when n ⁶ is 1, n ⁴ is an integer from 0 to 4. , When n ⁶ is 2, n ⁴ is an integer from 0 to 6.
n ⁷ is an integer from 0 to 7
n ⁸ is 1 or 2, ^{n 7} when ^{n 8} is 1 is an integer of 0 to 5, ^{n 7} when ^{n 8} is 2 is an integer of 0-7. )
^(R 1, ^{R 2} and ^{L 1} in the general formula (15) is selected from the same options as ^R 1, ^{R 2} and ^{L 1} in the general formula (1),
* Indicates a binding site with a compound represented by the general formulas (12) to (14). ) A resist composition containing the polymer according to any one of claims 1 to 5 . A step of forming a resist film on a substrate using the resist composition according to claim 6 and
The step of exposing the resist film using a particle beam or an electromagnetic beam, and
A method for manufacturing a device, which comprises a step of developing the exposed resist film to obtain a pattern. A step of applying the composition according to claim 6 onto a substrate to form a resist film, and
The step of irradiating the resist film with the first active energy ray and
The step of irradiating the resist film after the irradiation with the first active energy ray with the second active energy ray, and
Wherein the step of obtaining a second active energy beam resist film developed to the pattern after the irradiation, only contains the first active energy rays, a device manufacturing method is a particle beam or extreme ultraviolet radiation. When the first active energy ray is a particle beam, the second active energy ray is an electromagnetic wave, and when the first active energy ray is an extreme ultraviolet ray , the second active energy ray is the said first active energy ray. The method for manufacturing a device according to claim 8 , wherein the electromagnetic waves are longer than the wavelength of extreme ultraviolet rays . The method for manufacturing a device according to claim 8 or 9 , further comprising a step of heating with a heating wire or a laser between the step of irradiating the first active energy ray and the step of irradiating the second active energy ray. .. The first active species is generated from the composition in the resist membrane by the first activation energy ray irradiation.
The onium salt of the unit A is structurally changed by the first active species.
The method for producing a device according to any one of claims 8 to 10 , wherein a second active species is generated from the structurally changed onium salt by irradiation with the second active energy ray. The method for producing a device according to claim 11 , wherein the structurally changed onium salt is a ketone derivative.